Electron spin resonance spectra of marine and fresh-water manganese nodules

Eighty ferromanganese nodules from a wide variety of marine and fresh-water environments have been analyzed by electron spin resonance spectroscopy. The purpose has been to gain information on the forms in which the major constituents of manganese nodules are present. Contributions to ESR spectra of the nodules come mainly from Mn²⁺ and Fe³⁺. Deep-sea samples generally showed only broad resonance lines, and those with larger peaks close to g = 2.0 are believed to contain more Mn²⁺ than others. Some Antarctic and fresh-water nodules lack a strong Mn²⁺ resonance and have a peak around g = 4.0 which is most likely tetrahedral Fe³⁺. A number of smaller peaks in several samples could not be readily interpreted in terms of contributions from individual ionic species because of fundamental problems in preparing standards having the ion of interest in the same micro-environment as it experiences in the nodules.     

Magnetic phases in lunar fines: metallic Fe or ferric oxides?

The ferromagnetic resonance (g = 2.08 ± 0.03) observed for the Apollo 11 and 12 lunar fines is characterized by an asymmetric lineshape with a narrower appearance on the high field side. This asymmetry together with an anisotropy energy which varies from + 640 to + 500 G over the temperature range of 80 to 298 K indicates that the ferromagnetic resonance arises from metallic Pe having the body-centered cubic structure and not from hematite, magnetite or other Fe³⁺ ions in magnetite-like phases. The g-value, the lineshape asymmetry, and the temperature dependence of the linewidth for the Apollo 14 and 15 fines as reported by other workers are found to be essentially similar to those observed for the Apollo 11 and 12 fines, except a narrower linewidth is observed in the case of the Apollo 14 fines (600–650 G vs 700–800 G, at X-band and room temperature). This difference in linewidth is found to be correlated with the Ni and/or Co content in these samples. The ESR signal for the so-called ‘unknown ferric oxide’ phase of Griscom and Marquardt is also shown to have frequency and temperature dependences significantly different from those for the lunar fines.     

Natural iron-containing blue and colorless euclase studied by electron paramagnetic resonance

Natural blue and colorless rare-gem mineral specimens of euclase from Brazil are investigated by electron paramagnetic resonance (EPR). Angular dependences of Fe³⁺ EPR spectra in three mutually perpendicular crystal planes are analyzed revealing g and D tensors with significant low-symmetry effects, as for example, the high asymmetry parameter E/D = 0.28. Fourth-order degree Stevens parameters are also included in analysis. The anisotropy of both g and D tensors is consistent with Fe³⁺ substituting for Al³⁺ ions in strongly distorted AlO₅(OH) octahedra in which the oxygen distances range from 1.85 to 1.98 Å. Fe³⁺ is not responsible for the blue color because colorless and blue euclase show nearly the same Fe³⁺ concentration as measured by EPR. However, total iron content in blue sample is much higher than in the colorless one suggesting that the existing model that Fe²⁺–Fe³⁺ intervalence charge transfer transition may explain the blue color of euclase.     

Electron paramagnetic resonance study of iron(III) and manganese(II) in the glassy and crystalline environments of synthetic fayalite and tephroite

Crystals of the olivine minerals, tephroite (Mn₂SiO₄) and fayalite (Fe₂SiO₄) containing manganese(II) and iron (II and trace of III), respectively, were synthesized. Glasses were prepared from these crystalline materials by a splat-quench technique. Measurement of electron paramagnetic resonance (EPR) of all these powdered samples at room temperature show that the g-factors of Mn²⁺ in both glassy and crystalline environments (g_eff = 2.004) are the same, although the EPR linewidths (for glass, ΔH_pp = 200 G; for crystals ΔH_pp = 287 G) suggest less clustering of paramagnetic Mn²⁺ ions in the glass. Mn²⁺ probably occupies a distorted octahedral site in the tephroite crystal structure, although a four-fold coordination is suggested from other spectroscopic investigation on this glass. The EPR parameters of Fe³⁺ in synthetic fayalite glass (g_eff = 2.01 and 6.00; ΔH_pp=150 and 1375 G, respectively, for the high and low field resonances) and powdered crystals (g_eff = 3.31 and ΔH_pp = 900 G) indicated that Fe³⁺ ion in the crystals, is probably located in a distorted tetragonal site M2 and an axial environment has been proposed in the glassy system.     

Use of ultrasonically modulated electron resonance to study S-state ions in mineral crystals: Mn2+, Fe3+, in tremolite

The use of ultrasonically modulated electron resonance (UMER) to study S-state ions in substitutional sites of mineral single crystals is discussed. Mn²⁺ and Fe³⁺ in natural single crystals of tremolite are used as examples. Combined electron paramagnetic resonance (EPR) and UMER measurements establish almost certainly that Mn²⁺ enters predominantly into the distorted M4 sites occupied by Ca²⁺ in the ideal tremolite structure and only to a minor extent into the M1, M2 and M3 sites normally occupied by Mg²⁺. Fe³⁺ in tremolite gives rise to the well known high spin resonance with g _eff?4.3 but there is considerable uncertainty as to the site of the impurity ion.     

Distinct ruby suite at Sardapur, Orissa: A spectroscopic investigation

Orissa is an important area for gem variety of corundum deposits in India. Spectroscopic studies, such as ESR, OAS on samples from Sardapur, Orissa, were carried out to ascertain the colour cause of corundum. Electron spin resonance (ESR) spectroscopic study was carried out on the samples to detect the presence of paramagnetic ions i.e. Fe²⁺, Fe³⁺, Ti⁴⁺, Cr³⁺ and V³⁺ etc. The variable temperature experiment carried out to observe the effect of heating on peak valence state change in paramagnetic ions. Samples were cut and polished to obtain the optical absorption spectrum (OAS) to detect the colour causing transition ions/defect centres. The samples of gem variety were step heated up to 300°C for colour enhancement studies. EPMA analysis has revealed the low chromium concentration in the rubies. The varying hues of red in the corundum are due to the presence of bivalent and trivalent iron and charge transfer process along with Cr³⁺ absorption in the 550 nm region.     

Mössbauer spectra of kyanite,aquamarine, and cordierite showing intervalence charge transfer

The blue colors of several minerals and gems, including aquamarine (beryl, Be₃Al₂Si₆O₁₈) and cordierite (Al₃(Mg, Fe)₂Si₅AlO₁₈), have been attributed to charge transfer (CT) between adjacent Fe²⁺ and Fe³⁺ cations, while Fe²⁺→Ti⁴⁺ CT has been proposed for blue kyanites (Al₂SiO₅). Such assignments were based on chemical analyses and on polarization-dependent absorption bands measured in visible-region spectra. We have attempted to characterize the Fe cations in each of these minerals by Mössbauer spectroscopy (MS). In blue kyanites, significant amounts of both Fe²⁺ and Fe³⁺ were detected with MS, indicating that Fe²⁺→Fe³⁺ CT, Fe²⁺→Ti⁴⁺ CT, and Fe²⁺ and Fe³⁺ crystal field transitions each could contribute to the electronic spectra. In aquamarines, coexisting Fe²⁺ and Fe³⁺ ions were resolved by MS, supporting our assignment of the broad, relatively weak band at 16,100 cm^?1 in E∥c spectra to Fe²⁺→Fe³⁺ CT between Fe cations replacing Al³⁺ ions 4.6Å apart along c. A band at 17,500 cm^?1 in E⊥c spectra of cordierite is generally assigned to Fe²⁺ (oct)→Fe³⁺ (tet) CT between cations only 2.74 Å apart. However, no Fe³⁺ ions were detected in the MS at 293K of several blue cordierites showing the 17,500 cm^?1 band and reported to contain Fe³⁺. A quadrupole doublet with parameters consistent with tetrahedral Fe³⁺ appears in 77K MS, but the Fe³⁺/Fe²⁺ ratios from MS are much smaller than values from chemical analysis. These results sound a cautionary note when correlating Mössbauer and chemically determined Fe³⁺/Fe²⁺ ratios for minerals exhibiting Fe²⁺→Fe³⁺ CT.     

Temperature dependence on the electron paramagnetic resonance spectra of natural jasper from Taroko Gorge (Taiwan)

Structural properties of natural jasper from Taroko Gorge (Taiwan) have been investigated by means of powder X-ray diffraction, electron paramagnetic resonance (EPR) and Fourier transform infrared spectroscopic techniques. The EPR spectrum at room temperature exhibits a sharp resonance signal at g = 2.007 and two more resonance signals centered at g ≈ 4.3 and 14.0. The resonance signal at g = 2.007 has been attributed to the E′ center and is related to a natural radiation-induced paramagnetic defect. Two more resonance signals centered at g ≈ 4.3 and 14.0 are characteristic of Fe³⁺ ions. The EPR spectra recorded at room temperature of jasper samples, heat-treated at temperatures ranging from 473 to 1,473 K exhibit marked temperature dependence. The resonance signal corresponding to E′ center disappears at elevated temperatures. A broad, intense resonance signal centered at g ≈ 2.0 appears at elevated temperatures. This resonance signal is a characteristic of Fe³⁺ ions, which are present as hematite in the jasper sample. The intensity of the resonance signal becomes dominant at elevated temperatures at ≥873 K, masking g ≈ 4.3 and g ≈ 14.0 resonance signals. The EPR spectra of jasper heat-treated at 673 K have been recorded at temperatures between 123 and 296 K. The population of spin levels (N) has been calculated for the broad g ≈ 2.0 resonance signal. It is found that N decreases with decreasing temperature. The linewidth (ΔH) of g ≈ 2.0 resonance signal of the heat-treated jasper is found to increase with decreasing temperature. This has been attributed to spin–spin interaction of the Fe³⁺ ions present in the form of hematite in the studied jasper sample.     

Electron spin resonance of trivalent chromium in forsterite,Mg2SiO4

The electron spin resonance (ESR) spectrum of Cr³⁺ in a synthetic single crystal of forsterite doped with Cr₂O₃ was studied at room temperature in the X-band frequency range. The dependence of the observed spectra on the crystal orientation with respect to the applied magnetic field was investigated. The ESR spectra are described by the spin Hamiltonian \(H = \beta HgS + D(S_Z^{\text{2}} - {\text{1/3}}S{\text{(}}S{\text{ + 1)) + }}E{\text{(}}S_x^{\text{2}} - S_y^{\text{2}} {\text{)}}\) with S=3/2. The spin resonance reveals that the chromium ions are located at both the M1 and M2 positions. Other possible substitutional or interstitial Cr³⁺ positions may be possible, but were not observed. The site occupancy numbers of Cr³⁺ at M1 and M2 are roughly 1.2×10^?4 and 0.8×10^?4, respectively, assuming that chromium is oxidized completely. The preference of the chromium ions for M1 was interpreted qualitatively in terms of crystal field criteria. The rhombic and axial spin Hamiltonian parameters, D and E, and the directions of the magnetic axes obtained for M1 and M2 are consistent with the respective oxygen coordination polyhedra.     

Mössbauer spectra and magnetic features of ilvaites

Ilvaite samples from six different localities in Japan are found to be members of a solid-solution series varying from Ca(Fe²⁺,Fe³⁺)₂Fe²⁺(OH)O Si₂O₇ to approaximately Ca(Fe²⁺,Fe³⁺)₂Fe _0.5 ²⁺ Mn _0.5 ²⁺ (OH)O Si₂O₇, and have been studied by Mössbauer spectrometry and magnetic measurements. The variation in intensity of Mössbauer doublets confirms that Mn substitutes for Fe²⁺ in the M(B) cation site. An temperatures decreasing from 300 K to 4K, an abrupt change in the reciprocal mass magnetic susceptibility, 1/x _g, occurs about 120 K; 1/x _g depends linearly upon temperature above 120 K. This change, which is characterized by an unusual mode of decrease in 1/x _g, has been interpreted based on Mössbauer spectra at 80 K: the spectra of Fe²⁺ and Fe³⁺ in the M(A) site show Zeeman splitting, whereas those of Fe²⁺ in the M(B) site do not show the effect. This Mössbauer evidence suggests that magnetic spins of Fe in M(A) are in an ordered state, very likely of antiparallel coupling, whereas those of Fe in M(B) are randomly oriented, showing that below 120 K ilvaite has two different magnetic states for Fe ions. As there is a line of evidence that the spins of Fe in M(B) would take an ordered state at extremely low temperatures, ilvaite magnetism may be regarded as basically antiferromagnetic. The magnetic spins of Fe in M(A) and M(B) undergo magnetic transitions at different specific temperatures, thus giving as a whole unusual features of magnetism.     

EPR of V4+ and Fe3+ in titanites

EPR investigations of yellow-green titanites from four localities showed presence of V⁴⁺ and Fe³⁺. They were investigated at X-band and room temperature. For V⁴⁺ the principal values of the g matrix and ⁵¹V hyperfine splitting and the directions of their principal axes indicate presence of a VO²⁺ ion substituting for Ti. Due to a high zero-field splitting only approximate values of the fine structure parameters of Fe³⁺ could be determined. With directions of their principal axes very similar to those of V⁴⁺ this ion must also substitute for Ti. Unusually large linewidths for both ions with little variation for samples from different localities are ascribed to the reported domain structure of titanites and accumulation of impurities in the domain boundaries. While for Fe³⁺ a small variation of the fine structure parameters explains this broadening, for V⁴⁺ a distribution of g-factors equal to its total anisotropy must be responsible whereas the V=0 bond length is remarkably constant. Due to preferential incorporation of impurities in the grain boundaries a contribution of dipolar broadening cannot be excluded.     

Electron paramagnetic resonance studies on clinochlore from Longitudinal Valley area,northeastern Taiwan

A natural sample of clinochlore from the Longitudinal Valley area of northeastern Taiwan has been characterized by using the powder X-ray diffraction (XRD), differential thermal analysis and electron paramagnetic resonance (EPR) spectroscopic techniques. The lattice parameters of the monoclinic (IIb) clinochlore with the composition (Mg_2.988 Al_1.196 Fe_1.6845 Mn_0.026)_5.8945 (Si_2.559 Al_1.441)₄ O₁₀ (OH)₈ have been calculated from the powder XRD data and are found to be a = 5.347 Å, b = 9.223 Å, c = 14.250 Å, β = 97.2° and Z = 2. The thermal behaviour of the sample showed the typical behaviour of clinochlore with a hydroxyl content of 12.5 wt%. The EPR spectrum at room temperature exhibits two resonance signals centred at g ≈ 2.0 and g ≈ 8.0. The signal at g ≈ 2.0 shows a six-line hyperfine structure which is a characteristic of Mn²⁺ ions in octahedral symmetry. The resonance signal at g ≈ 8.0 is a characteristic of Fe³⁺ ions. The EPR spectra have also been recorded at different temperatures (123–295 K). The population of spin levels (N) has been calculated for g ≈ 2.0 and g ≈ 8.0 resonance signals. It is observed that N increases with decreasing temperature. From EPR spectra, the spin-Hamiltonian parameters have been evaluated. The zero-field splitting parameter (D) is found to be temperature dependent. The peak-to-peak width of the g ≈ 8.0 resonance signal is found to increase with decrease in temperature.     

Assessing the redox properties of iron-bearing clay minerals using homogeneous electrocatalysis

Iron-bearing clay minerals are ubiquitous in the environment and have been shown to play important roles in several biogeochemical processes. Previous efforts to characterize the Fe²⁺–Fe³⁺ redox couple in clay minerals using electrochemical techniques have been limited by experimental difficulties due to inadequate reactivity between clay minerals and electrodes. The current work overcomes this limitation by utilizing organic electron transfer mediators that rapidly transfer electrons with both the Fe-bearing clay minerals and electrodes. Here, an Fe-rich source clay mineral (ferruginous smectite, SWa-1) is examined with respect to what fraction of structural Fe participates in oxidation/reduction reactions and the relationship between bulk Fe²⁺/Fe³⁺ ratios to the reduction potential (E_h).     

Single crystal absorption spectra of synthetic Ti,Fe-substituted pyropes

Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, $f_{O_2 }$ in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from ² T _2g → ² E _g of octahedral Ti³⁺ ions. The splitting value of the excited ²E _g state, 6200 cm^-1, and the crystal field parameter of Ti³⁺ in pyrope Δ ₀ = 19 200 cm^-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm^-1 was interpreted as a Fe^2+[8] → Ti^4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10^-11,0 atm), which permits a fraction of Fe³⁺ to enter the garnet, show an additional Fe^2+[8] → Fe^3+[6] charge transfer band at 19800 cm^-1.     

Reliability of experimental partition coefficients in carbonate systems: Evidence for inhomogeneous distribution of impurity cations

Electron spin resonance (ESR) spectroscopy, thermal analysis and X-ray diffraction (XRD) analysis are used to study the mode of incorporation of a wide range of impurity ions (up to 1% Ni²⁺, Sr²⁺, Cd²⁺, Mg²⁺, Cu²⁺, Fe²⁺, Zn²⁺, Pb²⁺, Mn²⁺ and Ba²⁺) in calcites synthesised in aqueous solutions. It is shown that when certain impurity ions are incorporated in these calcites they become concentrated, together with other trace elements such as Mn²⁺, into hitherto unsuspected trace phases. The important conclusion is drawn that unless the scavenging of trace elements by these phases can be avoided or corrected for, any calcite—liquid partition coefficients measured may have limited significance. ESR spectroscopy has revealed the intense strain common in calcites grown by different methods, whilst thermal analysis suggested that such strain may significantly alter the thermodynamic properties of these calcites. ESR spectroscopic analysis of aragonites synthesised by methods previously reported in the literature has revealed the common occurrence of trace calcite at concentrations below the XRD detection limit and proves the tendency of this calcite to scavenge trace Mn. Using ESR spectroscopy to monitor trace calcite levels and structural imperfections in synthetic aragonites, the urea hydrolysis technique is modified to provide a method for the synthesis of high-purity strain-free aragonite available for experimental studies.     

Crystal field and charge transfer spectrum of (Mg, Fe)SiO3 majorite

Majorite of bulk composition Mg_0.86Fe_0.15SiO₃ was synthesized at 19 GPa and 1900 °C at an oxygen fugacity close to the Re/ReO₂ buffer. Optical absorption spectra of polycrystalline samples were measured from 4000 to 25000cm^?1. The following features were observed: (1) Three bands at 4554, 6005 and 8093 cm^?1 due to the ⁵E_g → ⁵T_2g transition of Fe²⁺ in a distorted dodecahedral site. (2) A band at 9340 cm^?1 due to the transition ⁵T_2g → ⁵E_g of octahedral Fe²⁺. (3) A band at 22784 cm^?1 resulting from Fe³⁺, probably in an octahedral site (⁶A_1g → ⁴A_1g, ⁴E_g). (4) A very intense system of Fe²⁺ → Fe³⁺ intervalence charge transfer bands which can be modelled by two Gaussian components centered at 16542 and 20128 cm^?1. The existence of two components in the charge transfer spectrum could be related to the fact that the tetragonal majorite structure may contain Fe³⁺ in two different octahedral sites. The crystal field splitting Δ of Fe²⁺ in dodecahedral coordination is 5717 cm^?1. If a splitting of the ground state in the order of 1000 cm^?1 is assumed, this yields a crystal field stabilization energy (CFSE) of 3930 cm^?1, comparable to the CFSE of Fe²⁺ in pyrope-rich garnet. However, the splitting of ⁵T_2g is significantly higher than in pyrope. This would be consistent with Fe²⁺ preferentially occupying the more distorted one of the two dodecahedral sites in the majorite structure. For octahedral Fe²⁺, Δ= 9340 cm^?1 and CFSE=3736 cm^?1, assuming negligible splitting of the ground state.     

Polarized electronic absorption spectra of synthetic (Mg,Fe)-orthopyroxenes,ferrosilite and Fe3+-bearing ferrosilite

The assignment of spin-allowed Fe²⁺-bands in orthopyroxene electronic absorption spectra is revised by studying synthetic bronzite (Mg_0.8 Fe_0.2)₂Si₂O₆, hypersthene (Mg_0.5 Fe_0.5)₂Si₂O₆ and ferrosilite (Fe₂Si₂O₆). Reheating of bronzite and hypersthene single crystals causes a redistribution of the Fe²⁺-ions over the M1 and M2 octahedra, which was determined by Mössbauer spectroscopy and correlated to the intensity change of the spin-allowed Fe²⁺ d-d bands in the polarized absorption spectra. The 11000 cm^-1 band is caused by Fe²⁺ in M1 (⁵B_2g→⁵A_1g) and Fe²⁺ in M2 (⁵A₁→⁵A₁), the 8500 cm^-1 band by Fe²⁺ in M1 (⁵B_2g→⁵B_1g) and the 5000 cm^-1 band by Fe²⁺ in M2 octahedra (⁵A₁→⁵B₁). The Fe²⁺-Fe³⁺ charge transfer band is identified at 12500cm^-1 in the spectra of synthetic Fe³⁺ -Al bearing ferrosilite. This band shows a strong γ-polarization and therefore is caused by Fe²⁺ -Fe³⁺-ions in edge-sharing octahedra.     

东北地区球粘土的地质特征和成矿条件

东北地区球粘土主要产于吉林省舒兰县、永吉县和黑龙江省牡丹江等地,属老第三纪,未固结成岩,主要由无序高岭石组成,无重结晶及有序化现象.常含少量有机质或与褐煤矿层等伴生.其可塑性、粘结性及干燥强度较好.球粘土的成矿主要受温湿气候、物质来源、搬运方式、沉积环境、构造及特定的时代、有机质的作用等条件控制.已知储量近2亿吨.     

57Fe NCR of Fe phases in “magnetic cassiterites”

A pyralspite garnet from an anomalously magnetic concentrate of a pegmatitic cassiterite ore has been investigated using ⁵⁷Fe nuclear gamma-ray resonance spectroscopy. The quadrupole splitting and isomer shift values of 3.6 mm/s and 1.4 mm/s, respectively, are among the largest observed for Fe²⁺ ions and indicate a very low covalency of the dodecahedral Fe²⁺ — O²-bonds. These data support the more recent and lower value (10.2–10.1 kcal/ mole) of White and Moore (1972) for the CFSE of the dodecahedral Fe²⁺ ion and suggest that the CFSE should be a useful approximation to the site preference energy of Fe²⁺ for this site.